Condensation of aromatic compounds with unsaturated organic compounds in the presence of mixed catalysts



?afented Aug. 31, 1954 CONDENSATION OF AROMATIC COMPOUNDS WITH UNSATURATED ORGANIC COM POUNDS IN THE PRESENCE OF MIXED CATALYSTS Herman Pines and Vladimir N. Ipatieff, Chicago,

111., assignors to Universal Oil Products Company, Chicago, 111., a. corporation of Delaware No Drawing, Application April 4, 1951, Serial No. 219,316

24 Claims. 1

This invention relates to the condensation of unsaturated organic compounds with aromatic compounds and to products formed thereby. This invention relates more particularly to the side chain alkylation with an olefin of an alkylaromatic hydrocarbon in which a carbon atom combined with the aromatic nucleus is also combined with at least one hydrogen atom. The process relates still more specifically to the side chain alkylation with ethylene of an alkylbenzene hydrocarbon having at least one hydrogen atom combined with a carbon atom in alpha position to the benzene ring.

The condensation of aromatic compounds with unsaturated organic compounds such as the alkylation of aromatic hydrocarbons with oleflnic hydrocarbons, has been the subject of many investigations over a long period of time. Many different catalysts have been used including various mineral acids and acid-acting compounds but in all of these reactions, nuclear condensation has always been effected. Thus in the acid catalyzed alkylation of aromatic compounds having attached to a carbon atom of the ring a saturated carbon atom to which is attached at least one hydrogen atom, the entering alkyl group attaches to the aromatic nucleus. No direct catalytic method of introducing the alkyl group into the side chain has been known. Heretofore we accomplished side chain alkylation of toluene and related alkylaromatic compounds by noncatalyzed thermal means as set forth in our copending application Serial Number 152,991 filed March 30, 1950, but this thermal alkylation process requires high temperatures and highpressures for its successful operation.

We have found that side chain alkylationof toluene and other carbocyclic aromatic andheterocyclic aromatic ring compoundshaving a nonolefinic double bond such as thiophenes, furan, pyridine, quinoline, pyrrole, etc. and having attached to a nuclear carbon atom a saturated carbon atom to which is attached at least one hydrogen atom may also be used as starting materials to efiect the side chain alkylation with an olefin at relatively lower temperatures and pressures in the presence of a catalyst comprising essentially an alkali metal and a heterocyclic compound promoter containing a ring consisting of a nitrogen atom and at least 4 and not more than 5 carbon atoms. If a heterocyclic compound is being subjected to side chain alkylation, a different heterocyclic compound is used as catalyst promoter. The carbon atom which is attached to the aromatic nucleus of said aromatic compounds is referred to as a saturated car"- bon atom because it is a part of a non-olefin-ic group such asan alkyl group, a cycloalkyl group, a cycloalkalkyl group and an aralkyl group containing no ethylenic bonds" or similar unsaturation. The carbon atom which is attached to an aromatic nucleus is thus apart of a saturated group including an alkyl group, a cycloalliyl group, and an aralkyl group (as a CsH5'-CH2- group) containing no olefinicun'saturation.

An object of this inventionis to react an urisaturated organic compoundwith an aromatic compound selected from the group consisting of carbocyelic and heterocyclic aromatic ringcompounds having attached to a nuclear carbon atom a non-olefinic or saturated carbon atom to which is attached at least one'hydrogen atom.

An additional object of this invention is to react a monoolefin with an alkylaromatic hydrocarbon to form an aromatic hydrocarbon with a longer alkyl group.

Another object of this invention is to condense ethylene with the side chain of an alkylaromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of said alkyl group to which is attached at least one hydrogen atom.

Still another object of this invention is to con dense ethylene with the alkyl side chain of an alkylbenzene hydrocarbon, said side chain containing an alpha carbon atom to which is attached a replaceable hydrogen atom.

A further object of this invention is to condense ethylene with the cycloalkyl group of a cycloalkylbenzene hydrocarbon, said cycloalkyl group having a hydrogen atom combined with the carbon atom of the' cycloalkyl group which is attached to the aromatic ring.

A still further object of this invention is to provide a process for the side chain alkylation of an alkylaromatic hydrocarbon.

A further object of this invention is to condense ethylene with a polycyclic hydrocarbon having at least one of the rings saturated and having at least one hydrogen atom combined with the carbon atom of the saturated ring which is attached to the aromatic ring.

An additional object of this invention is to provide a method for producing an aromatic compound containing a long hydrocarbon side chain, said compound being useful in the production of detergents, wetting agents and the like.

One embodiment of this invention relates t'oa process which comprises reacting a non-conju gated olefinic hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkalkyl group, and an aralkyl group and to which last named carbon atom is attached at least one hydrogen atom, the process being carried out at condensation conditions in the presence of an alkali metal and of a heterocyclic compound containing a ring consisting of a nitrogen atom and at least 4 and not more than 5 carbon atoms, and recovering the resultant condensation product.

A second embodiment of this invention relates to a process which comprises reacting a nonconjugated olefinic hydrocarbon and a carbocyclic aromatic ring compound having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and of an aromatic type heterocyclic compound containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

Another embodiment of this invention relates to a process which comprises reacting a monoolefin and an aromatic compound having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and of an aromatic type heterocyclic compound containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

Still another embodiment of this invention relates to a process for producing longer chain aromatic hydrocarbons which comprises reacting an alkene and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of an alkali metal and of an aromatic type heterocyclic compound containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

A further embodiment of this invention relates to a process for producing a longer chain benzene hydrocarbon which comprises reacting an alkene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and a pyridine, and recovering the resultant condensation product.

A still further embodiment of this invention relates to a process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and a pyridine, and recovering the resultant condensation product.

An additional embodiment of this invention relates to a process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially sodium and a pyridine, and recovering a longer chain benzene hydrocarbon from the resultant reaction products.

A still additional embodiment of this invention relates to a process which comprises catalytically reacting an olefinic hydrocarbon and an aromatic compound having a structure represented by the formula:

wherein Ar represents an aromatic radical having a' nucleus selected from carbocyclic nuclei and R and R each separately and independently represents a member of the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group and R, and R together represent a cycloalkyl group, the process being carried out at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and a heterocyclic compound containing a ring consisting of a nitrogen atom and at least 4 and not more than 5 carbon atoms, and

recovering the resultant condensation product.

Still another embodiment of this invention relates to a process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and a pyridine, and recovering normal propylbenzene from the resultant reaction product.

Still a further embodiment of this invention relates to a process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and an alkyl pyridine, and recovering normal propylbenzene from the resultant reaction product.

Another embodiment of this invention relates to a process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and a quinoline, and recovering normal propylbenzene from the resultant reaction products.

The compounds with which unsaturated organic compounds are condensed in our process comprise aromatic compounds having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group to which last named carbon atom is attached at least one hydrogen atom. By the term aromatic compound we mean to include not only alkylated benzenes, substituted benzenes, naphthalenes, and derivatives thereof, but also all compounds containing a stable ring or nucleus such as is present in benzene and which possesses unsaturation in the sense that benzene does, but which has no ethylenic unsaturation. The carbocyclic compounds may have a benzene, naphthalene, etc. nucleus. In addition, the aromatic compounds contemplated for use in our process may contain both a carbocyclic ring and a heterocyclic ring such as is found in indole and in carbazole.

Also, the aromatic compounds may contain both a benzene nucleus and a cycloalkane nucleus such as is found in tetralin and in indan.

As hereinbeforestated, the aromatic compounds preferred for use in our process contain a saturated side chain, said chain being attached to a nuclear carbon atom by a saturated carbon atom, i. e., a carbon atom that is bonded by univalent bonds to four atoms. The saturated car'- bon atom should have at least one hydrogen atom attached thereto. These requisites are desirable for the reason that aromatic compounds, such as t-butylbenzene, which do not have a hydrogen atom attached to the alpha carbon atom, show very little tendency under the conditions of operation employed in our process to undergo condensation of the type herein taught. Similarly, styrene, in which the alpha carbon atom in the side chain is unsaturated, does not condense with unsaturated organic compounds in the manner herein specified. Thus the preferred aromatic compounds are those in which the alpha carbon atom of the side chain is saturated.

and in which said alpha carbon atom has at least one hydrogen atom attached thereto. The side chain may comprise only one carbon atom, as the methyl group in toluene, or it may comprise a number of saturated carbon atoms in straight chain or branched chain relation such as the normal butyl radical or the isobutyl radical in normal butylbenzene and isobutylbenzene, respectively. The substituent need not necessarily be an aliphatic chain; it may be a cycloalkane radical as in tetralin or as in cyclohexylbenzene or an aralkyl group as a benzyl group as in diphenylmethane.

Suitable alkylaromatic hydrocarbons include toluene, ethylbenzene, normal propylbenzene, cumene, normal and secondary butylbenzene, methylnaphthalene, and the like. able aromatic hydrocarbons include tetralin, indan, diphenylmethane, cyclopentylbenzene, and methylethylbenzene.

The aromatic ring in the compounds herein referred to may contain other substituents such as a chloro group, a metho'xy group, an ethoxy group, a nitro group, and the like.

Other suit The aromatic reactants employed in our process are condensed with non-conjugated unsaturated organic compounds. The unsaturated organic compounds are olefinic in character and include monoolefins and. particularly ethylene; For the purposes of this invention, aromatic compounds such as benzene are not regarded as being unsaturated. Examples of unsaturated organic compounds suitable for use in this process include monooleflns such as ethylene, propylene, l-butene, Z-butene, and isobutylene, monoolefins of higher molecular weight: non-conjugated dienes such as 2,5-dimethyl-1,6-hexadiene and non-conjugated polyolefins containing more than two pairs of double bonds per molecule; unsaturated ketones such as mesityl oxide, and compounds such as allyl amine, allyl cyanide,

acrylonitrile, alpha cyanoacrylonitrile and the like.

Catalysts which are useful in this process include a combination of an alkali metal or alkali metals and a heterocyclic compound containing a ring consisting of a nitrogen atom and at least 4 but not more than 5 carbon atoms. Of the alkali metals: lithium, sodium, potassium, rubidium and cesium; the more plentiful sodium and potassium are generally preferred and particularly sodium because of its relatively lower cost. These alkali metals are utilized together with heterocyclic nitrogen compounds. The heterocyclic nitrogen compounds are preferably the aromatic type heterocycle nitrogen compounds containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms. The preferred heterocyclic compounds contain a ring consisting of a nitrogen atom and 5 carbon atoms with at least 1 of said carbon atoms combined with a single hydrogen atom and the other carbon atoms combined with a member of the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group or having 2 of the nuclear carbon atoms combined with an aromatic ring such as a benzene ring to form quinol-ine, or isoquinoline, or alkylated derivatives thereof. The heterocyclic nitrogen compounds which are preferred for use in this proce ess thus include pyridine, picoline, and other alkyl pyridines, quinoline, isoquinoline and various alkylated quinolines and isoquinolines. Also pyrrole which has a ring of 1 nitrogen atom and 4 carbon atoms is also utilizable as a catalyst constituent in this process. Saturated heterocyclic nitrogen compounds such as piperidine are also useful in this process.

Some of the heterocyclic nitrogen compounds which are utilizable in this process have the structural formulas and properties given in Table I. (See column '7.)

Better contacting of the reactants and catalysts and improved yields of desired products are sometimes effected by mixing the alkali metal and heterocyclic nitrogen compound with a catalyst supporting or spacing material such as activated charcoal; also granular coke, silica, alumina, pumice, porcelain, quartz, etc. steel turnings, copper shot, etc. which do not have an adverse influence on the reaction but improve the mixing. Such spacing materials are useful in either batch type operation as in an autoclave or continuous treatment in a tubular reactor or other suitable apparatus.

The process of this invention is carried out using either batch or continuous types of operation in suitable equipment such as autoclaves or tubular reactors constructed from steel or glass lined steel reactors. The process is carried out at a temperature of from about to about 350 C. and preferably at a temperature of from about 150 to about 275 C. at a pressure of from about 5 to about 50 atmospheres. When the stirring or mixing of the reactants and catalyst is very thorough and efficient, the process may be carried out readily at a temperature of -C. and at a pressure of 5 atmospheres, but higher temperatures and pressures are preferred when the mixing is less eificient. The operating temperature and pressure will also be dependent upon the aromatic and olefinic hydrocarbons charged and upon the ratios of reactants present in the reaction zone, as well as upon the catalyst present. The properties of catalysts and promoters used are not critical and depend on other factors such as temperature, hydrocarbons to be reacted, etc.

In order to promote the primary side chain alkylation, that is, to attach only one alkyl group to the alkyl side chain and in some instances to decrease the loss of olefin through undesired side reactions, it is generally preferred to employ an excess of aromatic hydrocarbon to olefin such as ethylene in this process. In other words, the preferred ratio of aromatic hydrocarbon to olefinic hydrocarbon is greater than one.

TABLE I Some heterocyclic nitrogen compounds Name Formula Sp. Gr. B. P., 0. M. P.. C.

Pyridine 0.98 20 0..... 115-6-; -42.

Plcollne (2-methyl pyrldine). 0. 95 15 O.. 128.8 -70.

O N 3-methyl pyridine 0 0. 96 15 0... 143. 6

Quinollnc 1. 09 20 0..... 237 747 111111.; 110- l9. 5.

Isoquinoline 1. 10 21 On... 24. 6 240. 763.

Pyrrole g 0. 95 20 0"... 128-130 HEII (3H HC-CH The amount of catalyst used in the process is dependent upon the nature and reactivity of the aromatic hydrocarbon undergoing side chain alkylation and upon the nature of the olefin used as alkylating agent. Also the articular heterocyclic nitrogen compound catalyst promoter has an influence upon the amount of alkali metal necessary for eflicient operation of the process. In general from about 0.05 to about 0.5 atomic proportion of alkali metal is present per molecular proportion of alkylaromatic hydrocarbon or other side chain alkylatable hydrocarbon present in the reaction zone. Also from about 0.01 to about mole per cent of heterocyclic nitrogen compound promoter is employed per molecular proportion of alkylaromatic hydrocarbon present in the reaction zone.

In carrying out the process the olefiriic hydrocarbon charged such as ethylene may be introduced continuously or intermittently, the latter method being commonly employed in the usual type of batch operation conducted in an autoclave solthat the consumption of ethylene can be followed by observing the decrease in operating pressure of the autoclave as the reaction progresses. After the reaction has reached the desired stage of completion, the reaction products are discharged from the autoclave, unconverted olefins such as ethylene is recovered for further use in the process or utilized for some other purpose. The mixture of reaction products is then subjected to suitable separation treatment such as filtration to remove unconsumed alkali metal catalyst followed by fractional distillation of normally liquid products to separate unconverted charging stock from side chain alkylated products and higher boiling materials, the latter being sometimes formed as by-products of the reaction. In some cases certain reaction products may be separated by fractional crystallization.

olefin such as ethylene and one molecular proportion of alkylaromatic hydrocarbon as toluene react in the presence of a catalyst such as sodium and a pyridine compound to form a longer chain alkylaromatic hydrocarbon as illustrated in the following equation:

C Ha

' Catalyst CH2=CH2 Toluene Ethylene n-Propylbenzene The resultant reaction product such as n-propylbenzene may sometimes react with a further molecular proportion of olefin as ethylene to form a still longer chain alkylaromatic hydrocarbon as indicated in the following equation:

+ CH2=CHa n-Propylbenzene Ethylene 3-Pl1enylpentane of the olefin.

The side chain alkylated compounds and particularly long chain alkylaromatic hydrocarbons formed in this process are useful as starting materials for the production of wetting agents,

In this process one molecular proportion of 40 synthetic detergents and the like. For example a long chain alkylbenzene hydrocarbon such as a tridecylbenzene which is produced by condensing normal butylbenzene or secondary butylbenzene with a nonylene fraction formed by polymerizing propylene in the presence of a solid phosphoric acid catalyst is a suitable starting material for detergent production. The tridecyl benzene is sulfonated with strong sulfuric acid to form tridecylbenzene sulfonic acid which is then neutralized with caustic soda, sodium bicarbonate or another alkaline material to form a salt of tridecylbenzene sulfonic acid, said salt being useful as a detergent for the washing of soiled cotton cloth and other materials. Some of the other condensation products formed by this process are also useable as intermediates in the production of chlorinated alkyl aryl hydrocarbons useful as insecticides and the condensation products may also be used as intermediates in the production of dyes, medicinals, etc.

The nature of this invention is illustrated further by the following examples which however should not be misconstrued to limit unduly the generally broad scope of the invention.

EXAMPLE I A glass lined rotatable steel autoclave of 850 cc. capacity was charged with 92 grams (1 mol) of toluene, 6-? grams of sodium and 2 grams of pyridine, after which the autoclave was closed and ethylene was then introduced to the autoclave through a control valve to a .pressure of 30 atmospheres. The charged autoclave containing the reaction mixture including the ethylene was then heated at a temperature of 200 to 230 C. for a time of 4 to 5 hours after which the autoclave was cooled to room temperature. The unconsumed ethylene was released through the control valve, the autoclave was then opened and the reaction product was removed therefrom. The reaction product was filtered to separate the used sodium from normally liquid products and the latter were then subjected to fractional distillation. In this way 21.6 grams of normal propylbenzene was recovered which represented 28% of the toluene charged in this run. The yield of normal propylbenzene was 18 mol per cent based upon the charged toluene and 64% based upon the toluene which reacted. Seven mol per cent of the toluene which reacted was also converted into the 3-phenylpentane.

EXAMPLE II The autoclave employed in Example I was charged similarly with 92 grams of toluene, 6-7 grams of sodium, 2 grams of 2-methylpyridine (alpha picoline) and ethylene to a pressure of 30 atmospheres. The charged autoclave was then heated at a temperature of 200 to 230 C. for a time of 4-5 hours. The reaction product was worked up in the same manner as that obtained in Example I to yield 12.7 grams of n-propylbenzene and 1 gram of E-phenylpentane. The yield of normal propylbenzene was 11% based on the toluene charged and 61 mol per cent based on the toluene which reacted.

We claim as our invention:

1. A process which comprises reacting a nonconjugated olefinic hydrocarbon and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having attached to a nuclear carbon atom a carbon atom of a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkallcyl group, and an aralkyl group and to which last named carbon atom is attached at least one hydrogen atom, the process being carried out at condensation conditions in the presence of an alkali metal-and of a heterocyclic compound different from the aforesaid aromatic reactant and containing a ring consisting of a nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

2. A process which comprises reacting a nonconjugated clefinic hydrocarbon and a carbocyclic aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and of an aromatic type heterocyclic compound containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

3. A process which comprises reacting a monoolefin and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and of an aromatic type heterocyclic compound containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

4. A process for producing longer chain aromatic hydrocarbons which comprises reacting an alkene and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of an alkali metal and of an arcmatic type heterocycli'c compound containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

- 5. A process for producing a longer chain benzene hydrocarbon which comprises reacting an alkene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and a pyridine, and recovering the resultant condensation product.

6. A process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and a pyridine, and recovering the resultant condensation product.

7. A process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially sodium and a pyridine, and recovering a longer chain benzene hydrocarbon from the resultant reaction products.

8. A process which comprises catalytically reacting an olefinic hydrocarbon and a carbocyclic aromatic compound having attached to a nuclear carbon atom thereof a carbon atom of a saturated hydrocarbon group and to which last-named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of a catalyst comprising essentially an alkali metal and a heterocyclic compound conttaining a ring consisting of a nitrogen atom and at least 4 and not more than carbon atoms, and recovering the resultant condensation product.

9. .A process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and a pyridine, and recovering normal propylbenzene from the resultant reaction product.

10. A process for producing normal prop-ylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and an alkyl pyridine, and recovering the normal propylbenzene from the resultant reaction product.

11. A process for producing normal propylbenzene which comprises reacting ethylene and toluene at a condensation temperature in the presence of a catalyst comprising essentially sodium and a quinoline, and recovering normal propylbenzene from the resultant reaction products.

12. A process which comprises reacting a nonconjugated olefinic hydrocarbon and an aromatic compound having attached to a nuclear carbon atom a carbon atom of a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkalkyl group, and an aralkyl group and. to which last named carbon atom is attached at least one hydrogen atom, the process being carried out at a temperature of from about 100 to about 350 C. in the presence of an alkali metal and of a heterocyclic compound different from the aforesaid aromatic reactant and containing a ring consisting of a nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

13. A process for producing longer chain aromatic hydrocarbons which comprises reacting an alkene and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a temperature of from about 100 to about 350 C. in the presence of an alkali metal and of an aromatic type heterocyclic compound containing a ring of 1 nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation prodnot.

14. A process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least 1 hydrogen atom at a temperature of from about 100 to about 350 C. in the presence of a catalyst comprising essentially an alkali metal and a pyridine, and recovering the resultant condensation product.

15. A process for producing a longer chain benzene hydrocarbon which comprises reacting ethylene and a benzene hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least 1 hydrogen atom at a temperature of from about to about 350 C. in the presence of a catalyst comprising essentially sodium and pyridine, and recovering a longer chain benzene hydrocarbon from the resultant reaction products.

16. A process which comprises catalytically reacting an olefinic hydrocarbon and a carbocyclic aromatic compound having attached to a nuclear carbon atom thereof a carbon atom of a saturated hydrocarbon group and to which last-named carbon atom is attached at least one hydrogen atom at a temperature of from about 100 to about 350 C. in the presence of a catalyst comprising essentially an alkali metal and a heterocyclic compound containing a ring consisting of a nitrogen atom and at least 4 and not more than 5 carbon atoms, and recovering the resultant condensation product.

17. A process which comprises catalytically reacting ethylene and a carbocyciic aromatic compound having attached to a nuclear carbon atom thereof a carbon atom of a saturated hydrocarbon group and to which last named carbon atom is attached at least one hydrogen atom at a temperature of from about 100 to about 350 C. in the presence of a catalyst comprising essentially an alkali metal and a heterocyclic compound containing a ring consisting of a nitrogen atom and at least 4 and not more than 5 carbon atoms, and recovering the resultant condensation product.

18. A process for producing normal propylbenzene which comprises reacting ethylene and toluene at a temperature of from about 100 to about 350 C. in the presence of a catalyst comprising essentially sodium and a pyridine, and recovering normal propylbenzene from th resultant reaction product.

19. A process for producing normal propylbenzene which comprises reacting ethylene and toluene at a temperature of from about 100 to about 350 C. in the presence of a catalyst comprising essentially sodium and an alkyl pyridine, and recovering the normal propylbenzene from the resultant reaction product.

20. A process for producing normal propylbenzene which comprises reacting ethylene and toluene at a temperature of from about 100 to about 350 C. in the presence of a catalyst comprising essentially sodium and a quinoline, and recovering normal propylbenaene from the resultant reaction product.

21. A process which comprises reacting ethylene and an aromatic compound selected from the group consisting of carbocyclic aromatic and heterocyclic aromatic ring compounds having at tached to a nuclear carbon atom a carbon atom of a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, a cycloalkalkyl group, and an aralkyl group and to which last-named carbon atom is attached at least one hydrogen atom, the process being carried out at condensation conditions in the presence of an alkali metal and of a heterocyclic compound different from the aforesaid aromatic reactant and containing a ring consisting of a nitrogen atom and at least 4 but not more than 5 carbon atoms, and recoverin the resultant condensation product.

22. .A process which comprises reacting ethylene and a carbocyclic aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last-named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and an aromatic type heterocyclic compound containing a ring of one nitrogen atom and at least 1 but not more than 5 carbon atoms, and recovering the resultant condensation product.

23. A process which comprises reacting ethylene in an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last-named carbon atom is attached at least one hydrogen atom at condensation conditions in the presence of an alkali metal and of an aromatic type heterocyclic compound containing a ring of one nitrogen atom and at least 4 but not more than 5 carbon atoms, and recovering the resultant condensation product.

24. A process for producing longer chain aromatic hydrocarbons which comprises reacting ethylene and an aromatic hydrocarbon having attached to a nuclear carbon atom a carbon atom of a saturated hydrocarbon group and to which last-named carbon atom is attached at least one hydrogen atom at a condensation temperature in the presence of an alkali metal and of an aromatic type heterocyciic compound containing a ring of one nitrogen atom and at least "1 but not more than 5 carbon atoms, and recovering the resultant condensation product.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,934,123 Hofmann et a1. Nov. '7, 1933 2,337,014 Crawford et a1. Dec. 14, 1943 i l 18,641 Whitman Sept. '7, 1948 2,548,803 Little Apr. 10, 1951 

1. A PROCESS WHICH COMPRISES REACTING A NONCONJUGATED OLEFINIC HYDROCARBON AND AN AROMATIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF CARBOCYCLIC AROMATIC AND HETEROCYCLIC AROMATIC RING COMPOUNDS HAVING ATTACHED TO A NUCLEAR CARBON ATOM A CARBON ATOM OF A HYDROCARBON GROUP SELECTED FROM THE GROUP CONSISTINGT OF AN ALKYL GROUP, A CYCLOALKYL GROUP, A CYCLOALKALKYL GROUP, AND AN ARALKYL GROUP AND TO WHICH LAST NAMED CARBON ATOM IS ATTACHED AT LEAST ONE HYDROGEN ATOM, THE PROCESS BEING CARRIED OUT AT CONDENSATION CONDITIONS IN THE PRESENCE OF AN ALKALI METAL AND OF A HETEROCYCLIC COMPOUND DIFFERENT FROM THE AFORESAID AROMATIC REACTANT AND CONTAINING A RING CONSISTING OF A NITROGEN ATOM AND AT LEAST 4 BUT NOT MORE THAN 5 CARBON ATOMS, AND RECOVERING THE RESULTANT CONDENSATION PRODUCT. 